Polycyclic, fused ring compounds, metal complexes and polymerization process

ABSTRACT

Compounds and metal complexes comprising a polycyclic, fused ring ligand or inertly substituted derivative thereof having up to 60 atoms other than hydrogen, said ligand comprising at least: (1) a cyclopentadienyl ring, (2) a 6, 7, or 8 membered ring other than a 6-carbon aromatic ring, and (3) an aromatic ring, with the proviso that said 6, 7, or 8 membered ring (2), is fused to both the cyclopentadienyl ring (1), and the aromatic ring (3), polymerization catalysts, a process to prepare the novel compounds and complexes, and olefin polymerization processes using the same are disclosed.

CROSS REFERENCE STATEMENT

This application claims the benefit of U.S. Provisional Application No.60/215,456, filed Jun. 30, 2000.

BACKGROUND OF THE INVENTION

This invention relates to a class of polycyclic, fused ring compounds,metal complexes formed therefrom, and to polymerization catalystsderived from such complexes that are particularly suitable for use in apolymerization process for preparing homopolymers and copolymers ofolefins or diolefins, including copolymers comprising two or moreolefins or diolefins such as copolymers comprising a monovinyl aromaticmonomer and ethylene.

Constrained geometry metal complexes and methods for their preparationare disclosed in U.S. Pat. No. 5,703,187. This publication also teachesthe preparation of certain novel copolymers of ethylene and a hinderedvinyl monomer, including monovinyl aromatic monomers, having apseudo-random incorporation of the hindered vinyl monomer therein.Additional teachings of constrained geometry catalysts may be found inU.S. Pat. Nos. 5,321,106, 5,721,185, 5,374,696, 5,470,993, 5,541,349,and 5,486,632, as well as WO97/15583, and WO97/19463.

Certain highly active, polyaromatic, metal complexes, especiallyderivatives of cyclopentaphenanthrenyl ligand groups are disclosed inU.S. Ser. No. 09/122,958, filed Jul. 27, 1998, (WO99/14221, publishedMar. 25, 1999). Despite the advance in the art occasioned by theforegoing cyclopentaphenanthrenyl containing metal complexes, it wouldbe desirable to provide improved metal complexes that do not containfused, polycyclic aromatic hydrocarbon functionality, in as much as thesame may be associated with potentially adverse biological activity.Accordingly, it would be desirable if there were provided metalcomplexes having similar or improved catalytic properties to theforegoing cyclopentaphenanthrenyl derivatives and also having improvedbiological properties. Metallocenes containing four fused rings arrangedon a central 5-membered carbon ring are disclosed in WO99/02540.

SUMMARY OF THE INVENTION

According to the present invention there is provided a polycyclic, fusedring compound corresponding to the formula: (Cp*)_(p)-M* (I) orCpM(Z)_(z)(X)_(x)(L)₁(X′)_(x′)(II), where Cp* is a polycyclic, fusedring ligand or inertly substituted derivative thereof comprising atleast: (1) a cyclopentadienyl ring, (2) a 6,7,or 8 membered ring otherthan a 6-carbon aromatic ring, and (3) an aromatic ring, with theproviso that said 6, 7, or 8 membered ring (2), is fused to both thecyclopentadienyl ring (1), and the aromatic ring (3), said Cp* having upto 60 atoms other than hydrogen;

p is 1 or 2;

when p is 1, M* is hydrogen, an alkali metal or an alkaline earth metalhalide, and, when p is 2, M* is an alkaline earth metal; said M* beingbound to at least one of the non-fused, ring-carbons of thecyclopentadienyl ring, (1);

Cp is the aromatic ligand group derived from Cp* by removal of M*;

M is a metal selected from Groups 3-10 or the Lanthanide series of thePeriodic Table of the Elements;

Z is either:

a) a cyclic ligand group containing delocalized π-electrons, including asecond or third, fused, polycyclic ligand, Cp, said Z being bonded to Mby means of delocalized π-electrons and optionally also covalentlybonded to Cp through a divalent bridging group, Z′, or

b) a divalent moiety of the formula -Z′Y—, wherein,

Z′ is SiR⁶ ₂, CR⁶ ₂, SiR⁶ ₂SiR⁶ ₂, CR⁶ ₂CR⁶ ₂, CR⁶═CR⁶, CR⁶ ₂SiR⁶ ₂,BR⁶, BR⁶L″, or GeR⁶ ₂;

Y is —O—, —S—, —NR⁵-, —PR⁵-; —NR⁵ ₂, or —PR⁵ ₂;

R⁵, independently each occurrence, is hydrocarbyl, trihydrocarbylsilyl,or trihydrocarbylsilylhydrocarbyl, said R⁵ having up to 20 atoms otherthan hydrogen, and optionally two R⁵ groups or R⁵ together with Y form aring system;

R⁶, independently each occurrence, is hydrogen, or a member selectedfrom hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenatedaryl, —NR⁵ ₂, and combinations thereof, said R⁶ having up to 20non-hydrogen atoms, and optionally, two R⁶ groups form a ring system;

L″ is a monodentate or polydentate Lewis base optionally bonded to R⁶;

X is hydrogen or a monovalent anionic ligand group having up to 60 atomsnot counting hydrogen;

L independently each occurrence is a neutral ligating compound having upto 20 atoms, other than hydrogen, and optionally L and X are bondedtogether;

X′ is a divalent anionic ligand group having up to 60 atoms other thanhydrogen;

z is 0, 1 or 2;

x is 0, 1, 2, or 3;

l is a number from 0 to 2, and

x′ is 0 or 1.

The above compounds may exist as isolated crystals, as a mixture withother compounds, in the form of a solvated adduct, dissolved in asolvent, especially an organic liquid solvent, in the form of a dimer,or as a chelated derivative, especially wherein the chelating agent isan organic material such as ethylenediaminetetraacetic acid (EDTA).

A further embodiment of the present invention includes a process forforming a cyclopentenone from a halogenated cyclic olefin by forming atrihydrocarbyl-substituted acetylenic derivative thereof and thereaftercarbonylating and ring closing the same to form the desiredcyclopentenone product. The cyclopentenone may be readily reduced anddehydrated to form the cyclopentadienyl substituted compounds, includingthose compounds of the present invention.

Also, according to the present invention, there is provided a catalystfor olefin polymerization comprising:

A. i) a metal complex of formula (II), and

ii) an activating cocatalyst,

the molar ratio of i) to ii) being from 1:10,000 to 100:1, or

B. the reaction product formed by converting a metal complex of formula(II) to an active catalyst by use of an activating technique.

Further according to the present invention there is provided a processfor the polymerization of olefins comprising contacting one or moreC₂₋₂₀ olefins, including cyclic olefins, under polymerization conditionswith a catalyst comprising:

A. i) a metal complex of formula (II), and

ii) an activating cocatalyst,

the molar ratio of i) to ii) being from 1:10,000 to 100:1, or

B. the reaction product formed by converting a metal complex of formula(II) to an active catalyst by use of an activating technique.

The present catalysts and polymerization processes are especiallyefficient for production of olefin homopolymers, copolymers of two ormore olefins, in particular, copolymers of ethylene and a vinylaromaticmonomer, such as styrene, and interpolymers of three or morepolymerizable monomers over a wide range of polymerization conditions,and especially at elevated temperatures. They are especially useful forthe formation of ethylene homopolymers, copolymers of ethylene and oneor more higher α-olefins (that is, olefins having 3 or more carbonatoms), copolymers of ethylene, propylene and a diene (EPDM copolymers),copolymers of ethylene and vinylaromatic monomers such as styrene (ESpolymers), copolymers of ethylene, styrene, and a diene (ESDM polymers),and copolymers of ethylene, propylene and styrene (EPS polymers).Examples of suitable diene monomers include ethylidenenorbornene,1,4-hexadiene or similar conjugated or nonconjugated dienes.Surprisingly, the metal complexes of formula (II) demonstrate equivalentor improved catalytic properties compared to metal complexes containingpolycyclic, fully aromatic, hydrocarbon ligands, and they and theirdegradation products are more biologically inert compared to compoundscontaining fused, polycyclic, fully aromatic hydrocarbon ligands.

The catalysts of this invention may also be supported on a solidmaterial and used in olefin polymerization processes in a slurry or inthe gas phase. The catalyst may be prepolymerized with one or moreolefin monomers in situ in a polymerization reactor or in a separateprocess with intermediate recovery of the prepolymerized catalyst priorto the primary polymerization process.

The compounds of formula (I) are useful in the formation of the metalcomplexes of formula (II) as well as in the preparation of other metalcomplexes. In addition to their use as polymerization catalysts,complexes according to the present invention may be used forhydroformulation, hydrogenation or oligomerization processes.

DETAILED DESCRIPTION OF THE INVENTION

All reference to the Periodic Table of the Elements herein shall referto the Periodic Table of the Elements, published and copyrighted by CRCPress, Inc., 1995. Also, any reference to a Group or Groups shall be tothe Group or Groups as reflected in this Periodic Table of the Elementsusing the IUPAC system for numbering groups. The contents of any patent,patent application or publication referenced herein is herebyincorporated by reference in its entirety herein, especially withrespect to its disclosure of organometallic structures, synthetictechniques and general knowledge in the art. As used herein the term“aromatic” refers to a polyatomic, cyclic, ring system containing (4δ+2)π-electrons, wherein δ is an integer greater than or equal to 1. Theterm “fused” as used herein with respect to two polyatomic, cyclic ringsmeans that such rings have two adjacent atoms thereof common to bothrings. The term “fused” as used herein with respect to a ring systemcontaining more than two polyatomic, cyclic rings, means that at leasttwo rings thereof are fused together.

Desirably, in the compounds of the invention, the ring (2) isa7-membered ring. Even more desirably, the cyclopentadienyl ring (1) andthe aromatic ring (3) are not fused together.

Preferred compounds of formula (I) of the invention are thosecorresponding to the formula:

structural isomers thereof wherein one or more double bonds occupydifferent positions within the various rings, and mixtures thereof,

wherein:

T independently each occurrence is carbon, silicon, nitrogen,phosphorus, oxygen, sulfur, or boron;

J independently each occurrence is hydrogen, hydrocarbyl,trihydrocarbylsilyl, trihydrocarbylgermyl, halide, hydrocarbyloxy,trihydrocarbylsiloxy, bis(trihydrocarbylsilyl)amino,di(hydrocarbyl)amino, hydrocarbyleneamino, hydrocarbylimino,di(hydrocarbyl)phosphino, hydrocarbylenephosphino, hydrocarbylsulfido,halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl,trihydrocarbylsilyl-substituted hydrocarbyl,trihydrocarbylsiloxy-substituted hydrocarbyl,bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylenephosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said J group having up to 40atoms not counting hydrogen atoms, and two J groups together may form adivalent derivative thereby forming a saturated or unsaturated ring,with the proviso that, in at least one occurrence, two or more of theforegoing J groups on different atoms, at least one of which is T,together form a divalent derivative, thereby forming at least onearomatic ring that is fused to the 6, 7, or 8 membered ring;

t is 0, 1 or 2; and, for compounds of formula (1A₁) or (1A₂) where T iscarbon, in at least one occurrence, t is 2; and

M* and p are as previously defined.

In the foregoing metal complexes of formula (I), although M* is depictedas being bonded to only one carbon atom of Cp, it is to be understoodthat when M* is not hydrogen, more than one such carbon atom of Cp mayshare such bond to M*. The metal complexes of formula (II) includecomplexes containing 1, 2, or 3 Cp groups, including those wherein twosuch Cp or other Z groups are bound together by a bridging group. Suchcomplexes are analogous structurally to metallocenes containing 1, 2 or3 cyclopentadienly groups, or inertly substituted derivatives thereof.Both symmetrical or unsymmetrical compounds are included, that is,compounds containing two dissimilar π-bonded groups, including thosecontaining two Cp groups or a Cp and a π-bonded Z group that is not a Cpgroup.

Preferred compounds (metal complexes) of formula (II) of the inventionare those corresponding to the formula:

wherein T, t, J, Z, M, X, L, X′, x, I, and X′ are as previously defined.

Such complexes include, in particular, complexes containing only one Cpgroup of the formulas:

as well a complexes containing 2 Cp groups of the formulas:

structural isomers thereof wherein one or more double bonds occupydifferent positions within the various rings, and mixtures thereof,

wherein T, J, t, M, Z′, X, L, X′, x, and X′ are as previously defined.

In the metal complexes, preferred L and L″ groups are carbon monoxide;phosphines, especially trimethylphosphine, triethylphosphine,triphenylphosphine and bis(1,2-dimethylphosphino)ethane; P(OR⁴)₃,wherein R⁴ is C₁₋₂₀ hydrocarbyl; ethers, especially tetrahydrofuran;amines, especially pyridine, bipyridine, tetramethylethylenediamine(TMEDA), and triethylamine; olefins; and neutral conjugated dieneshaving from 4 to 40, preferably 5 to 40 carbon atoms. Complexesincluding neutral diene L groups are those wherein the metal is in the+2 formal oxidation state.

Further in reference to the metal complexes, X preferably is selectedfrom the group consisting of hydro, halo, hydrocarbyl, silyl, andN,N-dialkylamino-substituted hydrocarbyl. The number of X groups dependson the oxidation state of M, whether Z is divalent or not and whetherany neutral diene groups or divalent X′ groups are present. The skilledartisan will appreciate that the quantity of the various substituentsand the identity of Z are chosen to provide charge balance, therebyresulting in a neutral metal complex. For example, when Z is divalent,and x is zero, X′ is two less than the formal oxidation state of M. WhenZ contains one neutral two electron coordinate-covalent bonding site,and M is in a formal oxidation state of +3, x may equal zero and X′equal 1, or x may equal 2 and X′ equal zero. In a final example, if M isin a formal oxidation state of +2, Z may be a divalent ligand group,whereupon x and x′ are both equal to zero and one neutral L ligand groupmay be present.

Highly preferred compounds of formula (I) correspond to the formula:

structural isomers thereof wherein one or more double bonds occupydifferent positions within the various rings, and mixtures thereof,

wherein J* independently each occurrence is hydrogen, hydrocarbyl,trihydrocarbylsilyl, trihydrocarbylgermyl, halide, hydrocarbyloxy,trihydrocarbylsiloxy, bis(trihydrocarbylsilyl)amino,di(hydrocarbyl)amino, hydrocarbyleneamino, hydrocarbylimino,di(hydrocarbyl)phosphino, hydrocarbylenephosphino, hydrocarbylsulfido,halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl,trihydrocarbylsilyl-substituted hydrocarbyl,trihydrocarbylsiloxy-substituted hydrocarbyl,bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylenephosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said J* group having up to40 atoms not counting hydrogen atoms, and two J* groups together or a J*and a J′ group together may form a divalent derivative thereby forming asaturated or unsaturated ring, with the proviso that, in at least oneoccurrence, two or more of the foregoing J* groups on different atoms,together form a divalent derivative, thereby forming at least onearomatic ring that is fused to the 6, 7, or 8 membered ring;

J′ independently each occurrence is hydrogen, hydrocarbyl,trihydrocarbylsilyl, trihydrocarbylgermyl, halide, hydrocarbyloxy,trihydrocarbylsiloxy, bis(trihydrocarbylsilyl)amino,di(hydrocarbyl)amino, hydrocarbyleneamino, hydrocarbylimino,di(hydrocarbyl)phosphino, hydrocarbylenephosphino, hydrocarbylsulfido,halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl,trihydrocarbylsilyl-substituted hydrocarbyl,trihydrocarbylsiloxy-substituted hydrocarbyl,bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylenephosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said J′ group having up to40 atoms not counting hydrogen atoms, and two J′ groups together or a J′group and a J* group together may form a divalent derivative therebyforming a saturated or unsaturated fused ring;

M* is hydrogen, an alkali metal or an alkaline earth metal halide,

T is carbon, boron, nitrogen or oxygen,

t is 1 or 2; and

t′ is 0, 1 or 2.

The corresponding preferred compounds of formula (II) are of theformula:

structural isomers thereof wherein one or more double bonds occupydifferent positions within the various rings, and mixtures thereof,

wherein Z, M, X, L, X′, x, ., x′, T, J*, J′, t, and t′ are as previouslydefined

More highly preferred compounds and metal complexes according to thepresent invention correspond to the formulas:

wherein

T is carbon, or nitrogen;

when T is carbon, t′ is 2, and when T is nitrogen, t′ is 1;

M* is hydrogen, sodium, potassium or lithium;

M is titanium;

R¹ each occurrence is hydrogen or a hydrocarbyl, hydrocarbyloxy,dihydrocarbylamino, hydrocarbyleneamino, dihydrocarbylamino-substitutedhydrocarbyl group, or hydrocarbyleneamino-substituted hydrocarbyl groupof up to 20 atoms not counting hydrogen, and optionally two R¹ groupsmay be joined together;

Y is —O—, —S—, —NR⁵-, —PR⁵-; —NR⁵ ₂, or —PR⁵ ₂;

Z′ is SiR⁶ ₂, CR⁶ ₂, SiR⁶ ₂SiR⁶ ₂, CR⁶ ₂CR⁶ ₂, CR⁶═CR⁶, CR⁶ ₂SiR⁶ ₂,BR⁶, BR⁶L″, or GeR⁶ ₂;

R⁵ each occurrence is independently hydrocarbyl, trihydrocarbylsilyl, ortrihydrocarbylsilylhydrocarbyl, said R⁵ having up to 20 atoms other thanhydrogen, and optionally two R⁵ groups or R⁵ together with Y form a ringsystem;

R⁶ each occurrence is independently hydrogen, or a member selected fromhydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl,—NR⁵ ₂, and combinations thereof, said R⁶ having up to 20 non-hydrogenatoms, and optionally, two R⁶ groups form a ring system;

X, L, and X′ are as previously defined;

x is 0, 1 or 2;

l is 0 or 1; and

X′ is 0 or 1;

with the proviso that:

when x is 2, X′ is zero, M is in the +4 formal oxidation state (or M isin the +3 formal oxidation state if Y is —NR⁵ ₂ or —PR⁵ ₂), and X is ananionic ligand selected from the group consisting of halide,hydrocarbyl, hydrocarbyloxy, di(hydrocarbyl)amido,di(hydrocarbyl)phosphido, hydrocarbylsulfido, and silyl groups, as wellas halo-, di(hydrocarbyl)amino-, hydrocarbyloxy-, anddi(hydrocarbyl)phosphino-substituted derivatives thereof, said X grouphaving up to 30 atoms not counting hydrogen,

when x is 0 and X′ is 1, M is in the +4 formal oxidation state, and X′is a dianionic ligand selected from the group consisting ofhydrocarbadiyl, oxyhydrocarbylene, and hydrocarbylenedioxy groups, saidX group having up to 30 nonhydrogen atoms,

when x is 1, and X′ is 0, M is in the +3 formal oxidation state, and Xis a stabilizing anionic ligand group selected from the group consistingof allyl, 2-(N,N-dimethylamino)phenyl,2-(N,N-dimethylaminomethyl)phenyl, and 2-(N,N-dimethylamino)benzyl, and

when x and X′ are both 0, I is 1, M is in the +2 formal oxidation state,and L is a neutral, conjugated or nonconjugated diene, optionallysubstituted with one or more hydrocarbyl groups, said L having up to 40carbon atoms and being bound to M by means of delocalized π-electronsthereof.

Most highly preferably, R¹ each occurrence is hydrogen,

Z is NR⁵ wherein R⁵ is C₁₋₁₀ alkyl or cycloalkyl; and

Z′ is dimethylsilane; with the proviso that:

when x is 2, 1 and X′ are both zero, M is in the +4 formal oxidationstate, and X is independently each occurrence methyl, benzyl, or halide;

when x and 1 are zero, X′ is one, and M is in the +4 formal oxidationstate, X′ is a 1,4-butadienyl group that forms a metallocyclopentenering with M,

when x is 1, I and X′ are zero, M is in the +3 formal oxidation state,and X is 2-(N,N-dimethylamino)benzyl; and

when x and X′ are 0, 1 is 1, M is in the +2 formal oxidation state, andL is 1,4-diphenyl-1,3-butadiene or 1,3-pentadiene.

Specific examples of metal complexes of formula (I) are:

Specific examples of metal complexes of formula (II) are:

The present process for forming a polycyclic, fused ring cyclopentadienecompound (III), in a preferred embodiment involves the following steps:

A) contacting

1) a cyclic compound containing ethylenic unsaturation in the ringforming atoms thereof and substituted at the α-position of suchethylenic unsaturation with a leaving group with

2) an acetylenic compound containing a protecting group at one of theacetylenic carbons and a group that is reactive with the leaving groupof the cyclic compound at the remaining acetylenic carbon underconditions to cause ligand exchange, optionally in the presence of abase, thereby forming a cyclic compound containing ethylenicunsaturation and substituted at an α-carbon of the ethylenicunsaturation with an acetylenic group;

B) carbonylating and ring closing the product of step A) to form apolycyclic, fused ring cyclopentenone compound; and

C) reducing and dehydrating the product of step B) to form the desiredpolycyclic, fused ring cyclopentadiene compound (III).

While the present process is applicable to the preparation of a widevariety of polycyclic, fused ring cyclopentadiene compounds, preferredproducts are those previously disclosed as being novel.

The process is further illustrated schematically as follows:

where Le is a leaving group, preferably halogen, most preferably Br,

Pr is a protecting group, preferably tri(C₁₋₁₀ hydrocarbyl)silyl, morepreferably SiR² ₃, where R² is C₁₋₁₀ alkyl or cycloalkyl, and mostpreferably R² is C₁₋₄ alkyl,

T″—T″ is the divalent remnant of the cyclic compound containingethylenic unsaturation excluding the carbons forming the ethylenicunsaturation and Le, and

M** is a group that is reactive with the leaving group, Le, preferablyan alkali metal, an alkaline earth metal halide or an alkaline earthmetal hydrocarbyl.

Desirably, the present process may be employed to prepare polycyclic,fused ring cyclopentadiene compounds (III) in which one of the ringsfused to the cyclopentadiene group is not an aromatic ring, preferablyone that contains 7 or more ring atoms, preferably carbons. Moredesirably still, the compounds prepared by the present process compriseboth the foregoing, non-aromatic ring containing 7 or more ring atomsand at least one aromatic ring fused thereto. Even more desirably thecyclopentadiene ring and the aromatic rings are not fused together.

Preferred cyclic compounds containing ethylenic unsaturation used instep 1) of the present process correspond to the formula:

T independently each occurrence is carbon, silicon, nitrogen,phosphorus, oxygen, sulfur, or boron;

J independently each occurrence is hydrogen, hydrocarbyl,trihydrocarbylsilyl, trihydrocarbylgermyl, halide, hydrocarbyloxy,trihydrocarbylsiloxy, bis(trihydrocarbylsilyl)amino,di(hydrocarbyl)amino, hydrocarbyleneamino, hydrocarbylimino,di(hydrocarbyl)phosphino, hydrocarbylenephosphino, hydrocarbylsulfido,halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl,trihydrocarbylsilyl-substituted hydrocarbyl,trihydrocarbylsiloxy-substituted hydrocarbyl,bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylenephosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said J group having up to 40atoms not counting hydrogen atoms, and optionally two J groups togethermay form a divalent derivative thereby forming a saturated orunsaturated ring;

In a preferred embodiment, in the foregoing formulas t is 0, 1 or 2;and, for compounds of formula 1A₁) or 1A₂) where T each occurrence iscarbon, in at least one occurrence, t is 2. In an even more preferredembodiment, in at least one occurrence, two or more of the foregoing Jgroups on different atoms, at least one of which is T, together form adivalent derivative, thereby forming at least one aromatic ring that isfused to the 6, 7, or 8 membered ring.

The initial cyclic, ethylenically unsaturated reagents 1) are knowncompounds or may be prepared according to well known techniques fromknown compounds. The cyclopentenone formation, step A), is similar tothe process disclosed in J. Org. Chem., 1988, 53, 2493, and ispreferably conducted at temperatures from 0 to 100° C., pressures from50 kPa to 5000 kPa, in an inert diluent. The optional base is preferablya Lewis base compound, especially an organic amine, an organicphosphine, or a mixture thereof. A catalyst, especially a palladium orplatinum halide or a mixture thereof in combination with a reducedcopper salt, that is a Cu(II) salt, may also be employed as well.Reaction times from a few minutes to several hours are normally used. Ahighly desirably acetylenic reagent 2) is (trimethylsilyl)acetylene.

The carbonylation and ring closure, step B), is desirably conducted atelevated pressures and temperatures in the presence of carbon monoxideand a metal catalyst, especially a platinum or rhodium salt. Suitabletemperatures are from 50° C. to 250° C. Suitable pressures are from 500kPa to 20 MPa, preferably from 1 MPa to 10 MPa. The reaction isdesirably conducted in an aqueous diluent also comprising one or moreLewis base compounds, especially organic amines, phosphines, or mixturesthereof. Reaction times of one to 20 hours are normally used.

The reduction and dehydration processes comprising step C) arepreferably conducted sequentially and may or may not involve recoveryand purification of the intermediate, reduced product prior todehydration. Suitable conditions of temperature and pressure are from 0°C. to 100° C. and from 50 kPa to 5000 kPa. A suitable reaction medium isa mixture of a chlorinated hydrocarbon and an alcohol. A preferredreducing agent is sodium borohydride. Reaction times from 15 minutes to20 hours may be employed. Dehydration is accomplished by use of milddehydrating conditions, such as contacting with dilute aqueous HCl attemperatures from 0° C. to 100° C. and pressures from 50 kPa to 5000kPa. The product is generally soluble in hydrocarbons orchlorohydrocarbons and is readily recovered by extraction with such asolvent followed by removal of solvent.

Specific examples of compounds of formula (III) prepared according tothe invention are:

Formation of metal complexes from the neutral polycyclic, fused ringcyclopentadiene compounds (III) is straightforward, using standardtechniques of ligand formation and organometallic synthesis. Preferablyit is readily accomplished by contacting the neutral compound with analkalimetal hydrocarbyl compound, an alkaline earth metal dihydrocarbylcompound, or an alkaline earth metal hydrocarbyl halide compound,followed by reaction with a transition metal halide or amide in an inertdiluent. Ligand groups, such as silaneamido functionality may be addedto the polycyclic, fused ring cyclopentadiene compounds prior toaddition of the transition metal where required. Optionally a reducingagent can be employed to produce the lower oxidation state complexes,and standard ligand exchange procedures can by used to produce differentligand substituents. Processes that are suitably adapted for use hereinare well known to synthetic organometallic chemists.

The foregoing syntheses are preferably conducted in a suitablenoninterfering solvent at a temperature from −100 to 300° C., preferablyfrom −78 to 100° C., most preferably from 0 to 50° C. By the term“reducing agent” herein is meant a metal or compound which, underreducing conditions causes the metal M, to be reduced from a higher to alower oxidation state. Examples of suitable metal reducing agents arealkali metals, alkaline earth metals, aluminum and zinc, alloys ofalkali metals or alkaline earth metals such as sodium/mercury amalgamand sodium/potassium alloy. Examples of suitable reducing agentcompounds are sodium naphthalenide, potassium graphite, lithium alkyls,lithium or potassium alkadienyls; and Grignard reagents. Most preferredreducing agents are the alkali metals or alkaline earth metals,especially lithium and magnesium metal.

Suitable reaction media for the formation of the complexes includealiphatic and aromatic hydrocarbons, ethers, and cyclic ethers,particularly branched-chain hydrocarbons such as isobutane, butane,pentane, hexane, heptane, octane, and mixtures thereof; cyclic andalicyclic hydrocarbons such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof; aromaticand hydrocarbyl-substituted aromatic compounds such as benzene, toluene,and xylene, C₁₋₄ dialkyl ethers, C₁₋₄ dialkyl ether derivatives of(poly)alkylene glycols, and tetrahydrofuran. Mixtures of the foregoingare also suitable.

Illustrative polycyclic cyclopentadiene compounds that may be preparedaccording to the present invention include: azulene, hexahydroazulene,2,4-dimethylazulene, 2,4-dimethylhexahydroazulene,2,8-dihydrodibenzo[e,h]azulene, and mixtures thereof, especiallymixtures of positional isomers.

Illustrative metal complexes that may be employed in the practice of thepresent invention include:

(2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidetitanium (II) 1,4-diphenyl-1,3-butadiene,

(2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidetitanium (II) 1,3-pentadiene,

((2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidetitanium (III) 2-(N,N-dimethylamino)benzyl,

(2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidetitanium (IV) dichloride,

2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidetitanium (IV) dimethyl,

2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidetitanium (IV) dibenzyl,

(2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(cyclohexyl)dimethyl-silanamidetitanium (II) 1,4-diphenyl-1,3-butadiene,

(2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(cyclohexyl)dimethyl-silanamidetitanium (II) 1,3-pentadiene,

((2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(cyclohexyl)dimethyl-silanamidetitanium (III) 2-(N,N-dimethylamino)benzyl,

(2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(cyclohexyl)dimethyl-silanamidetitanium (IV) dichloride,

2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(cyclohexyl)dimethyl-silanamidetitanium (IV) dimethyl,

2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(cyclohexyl)dimethyl-silanamidetitanium (IV) dibenzyl,

(2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidetitanium (II) 1,4-diphenyl-1,3-butadiene,

(2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidetitanium (II) 1,3-pentadiene,

((2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidetitanium (III) 2-(N,N-dimethylamino)benzyl,

(2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidetitanium (IV) dichloride,

2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidetitanium (IV) dimethyl,

2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidetitanium (IV) dibenzyl,

(2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(cyclohexyl)dimethyl-silanamidetitanium (II) 1,4-diphenyl-1,3-butadiene,

(2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(cyclohexyl)dimethyl-silanamidetitanium (II) 1,3-pentadiene,

((2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(cyclohexyl)dimethyl-silanamidetitanium (III) 2-(N,N-dimethylamino)benzyl,

(2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(cyclohexyl)dimethyl-silanamidetitanium (IV) dichloride,

2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(cyclohexyl)dimethyl-silanamidetitanium (IV) dimethyl,

2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(cyclohexyl)dimethyl-silanamidetitanium (IV) dibenzyl, and mixtures thereof, especially mixtures ofpositional isomers.

The skilled artisan will recognize that additional members of theforegoing list, obtainable by substitution of known ligands or differentGroup 3-10 metals for those specifically named, are also included withinthe invention. Moreover, it should also be recognized that all possibleelectronic distributions within the molecule, such as η³, η⁴ or η⁵ areintended to be included by the foregoing named compounds.

The complexes can be prepared by combining a metal halide salt with thecorresponding fused, polycyclic ring system ligand dianion in an inertdiluent, or by combining a metal amide with the corresponding neutralfused, polycyclic ring system in an inert diluent. Optionally a reducingagent can be employed to produce the lower oxidation state complexes,and standard ligand exchange procedures can by used to produce differentligand substituents. Processes that are suitably adapted for use hereinare well known to synthetic organometallic chemists. The syntheses arepreferably conducted in a suitable noninterfering solvent at atemperature from −100 to 300° C., preferably from −78 to 100° C., mostpreferably from 0 to 50° C. By the term “reducing agent” herein is meanta metal or compound which, under reducing conditions causes the metal M,to be reduced from a higher to a lower oxidation state. Examples ofsuitable metal reducing agents are alkali metals, alkaline earth metals,aluminum and zinc, alloys of alkali metals or alkaline earth metals suchas sodium/mercury amalgam and sodium/potassium alloy. Examples ofsuitable reducing agent compounds are sodium naphthalenide, potassiumgraphite, lithium alkyls, lithium or potassium alkadienyls; and Grignardreagents. Most preferred reducing agents are the alkali metals oralkaline earth metals, especially lithium and magnesium metal.

Suitable reaction media for the formation of the complexes includealiphatic and aromatic hydrocarbons, ethers, and cyclic ethers,particularly branched-chain hydrocarbons such as isobutane, butane,pentane, hexane, heptane, octane, and mixtures thereof; cyclic andalicyclic hydrocarbons such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof, aromaticand hydrocarbyl-substituted aromatic compounds such as benzene, toluene,and xylene, C₁₋₄ dialkyl ethers, C₁₋₄ dialkyl ether derivatives of(poly)alkylene glycols, and tetrahydrofuran. Mixtures of the foregoingare also suitable.

The complexes are rendered catalytically active by combination with anactivating cocatalyst or use of an activating technique, such as thosethat are previously known in the art for use with Group 4 metal olefinpolymerization complexes. Suitable activating cocatalysts for use hereininclude polymeric or oligomeric alumoxanes, especially methylalumoxane,triisobutyl aluminum modified methylalumoxane, or isobutylalumoxane;neutral Lewis acids, such as C₁₋₃₀ hydrocarbyl substituted Group 13compounds, especially tri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boroncompounds and halogenated (including perhalogenated) derivativesthereof, having from 1 to 10 carbons in each hydrocarbyl or halogenatedhydrocarbyl group, more especially perfluorinated tri(aryl)boroncompounds, and most especially tris(pentafluorophenyl)borane;nonpolymeric, compatible, noncoordinating, ion forming compounds(including the use of such compounds under oxidizing conditions),especially the use of ammonium-, phosphonium-, oxonium-, carbonium-,silylium- or sulfonium-salts of compatible, noncoordinating anions, orferrocenium salts of compatible, noncoordinating anions; bulkelectrolysis (explained in more detail hereinafter); and combinations ofthe foregoing activating cocatalysts and techniques. A preferred ionforming compound is a tri(C₁₋₂₀-hydrocarbyl)ammonium salt of atetrakis(fluoroaryl)borate, especially atetrakis(pentafluorophenyl)borate. The foregoing activating cocatalystsand activating techniques have been previously taught with respect todifferent metal complexes in the following references: EP-A-277,003,U.S. Pat. No. 5,153,157, U.S. Pat. No. 5,064,802, U.S. Pat. No.5,321,106, U.S. Pat. No. 5,721,185, U.S. Pat. No. 5,350,723, U.S. Pat.No. 5,425,872, U.S. Pat. No. 5,625,087, U.S. Pat. No. 5,883,204, U.S.Pat. No. 5,919,983, U.S. Pat. No. 5,783,512, WO 99/15534, and U.S. Ser.No.09/251,664, filed Feb. 17, 1999 (WO99/42467).

Combinations of neutral Lewis acids, especially the combination of atrialkylaluminum compound having from 1 to 4 carbons in each alkyl groupand a halogenated tri(hydrocarbyl)boron compound having from 1 to 20carbons in each hydrocarbyl group, especiallytris(pentafluorophenyl)borane, further combinations of such neutralLewis acid mixtures with a polymeric or oligomeric alumoxane, andcombinations of a single neutral Lewis acid, especiallytris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxaneare especially desirable activating cocatalysts. Preferred molar ratiosof Group 4 metal complex:tris(pentafluoro-phenylborane:alumoxane arefrom 1:1:1 to 1:10:30, more preferably from 1:1:1.5 to 1:5:10.

Suitable ion forming compounds useful as cocatalysts in one embodimentof the present invention comprise a cation which is a Bronsted acidcapable of donating a proton, and a compatible, noncoordinating anion,A⁻. As used herein, the term “noncoordinating” means an anion orsubstance which either does not coordinate to the Group 4 metalcontaining precursor complex and the catalytic derivative derivedtherefrom, or which is only weakly coordinated to such complexes therebyremaining sufficiently labile to be displaced by a neutral Lewis base. Anoncoordinating anion specifically refers to an anion which whenfunctioning as a charge balancing anion in a cationic metal complex doesnot transfer an anionic substituent or fragment thereof to said cationthereby forming neutral complexes. “Compatible anions” are anions whichare not degraded to neutrality when the initially formed complexdecomposes and are noninterfering with desired subsequent polymerizationor other uses of the complex.

Preferred anions are those containing a single coordination complexcomprising a charge-bearing metal or metalloid core which anion iscapable of balancing the charge of the active catalyst species (themetal cation) which may be formed when the two components are combined.Also, said anion should be sufficiently labile to be displaced byolefinic, diolefinic and acetylenically unsaturated compounds or otherneutral Lewis bases such as ethers or nitrites. Suitable metals include,but are not limited to, aluminum, gallium, niobium or tantalum. Suitablemetalloids include, but are not limited to, boron, phosphorus, andsilicon. Compounds containing anions which comprise coordinationcomplexes containing a single metal or metalloid atom are, of course,well known and many, particularly such compounds containing a singleboron atom in the anion portion, are available commercially.

Preferably such cocatalysts may be represented by the following generalformula:

(L*-H)_(d) ⁺ (A)^(d−)

wherein:

L* is a neutral Lewis base;

(L*-H)⁺ is a conjugate Bronsted acid of L*;

A^(d−) is a noncoordinating, compatible anion having a charge of d-, and

d is an integer from 1 to 3.

More preferably A^(d−) corresponds to the formula: [M′Q₄]⁻;

wherein:

M′ is boron or aluminum in the +3 formal oxidation state; and

Q independently each occurrence is selected from hydride, dialkylamido,halide, hydrocarbyl, hydrocarbyloxide, halo-substituted hydrocarbyl,halo-substituted hydrocarbyloxy, and halo-substituted silylhydrocarbylradicals (including perhalogenated hydrocarbyl-perhalogenatedhydrocarbyloxy- and perhalogenated silylhydrocarbyl radicals), said Qhaving up to 20 carbons with the proviso that in not more than oneoccurrence is Q halide. Examples of suitable hydrocarbyloxide Q groupsare disclosed in U.S. Pat. No. 5,296,433.

In a more preferred embodiment, d is one, that is, the counter ion has asingle negative charge and is A-. Activating cocatalysts comprisingboron which are particularly useful in the preparation of catalysts ofthis invention may be represented by the following general formula:

(L*-H)⁺(BQ₄)⁻;

wherein:

L* is as previously defined;

B is boron in a formal oxidation state of 3; and

Q is a hydrocarbyl-, hydrocarbyloxy-, fluorohydrocarbyl-,fluorohydrocarbyloxy-, hydroxyfluorohydrocarbyl-,dihydrocarbylaluminumoxyfluorohydrocarbyl-, or fluorinatedsilylhydrocarbyl-group of up to 20 nonhydrogen atoms, with the provisothat in not more than one occasion is Q hydrocarbyl. Most preferably, Qis each occurrence a fluorinated aryl group, especially, apentafluorophenyl group.

Preferred Lewis base salts are ammonium salts, more preferablytrialkyl-ammonium- or dialkylarylammonium-salts containing one or moreC₁₂₋₄₀ alkyl groups. The latter cocatalysts have been found to beparticularly suitable for use in combination with not only the presentmetal complexes but other Group 4 metallocenes as well.

Illustrative, but not limiting, examples of boron compounds which may beused as an activating cocatalyst in the preparation of the improvedcatalysts of this invention (as well as previously known Group 4 metalcatalysts) are

tri-substituted ammonium salts such as:

trimethylammonium tetrakis(pentafluorophenyl) borate,

triethylammonium tetrakis(pentafluorophenyl) borate,

tripropylammonium tetrakis(pentafluorophenyl) borate,

tri(n-butyl)ammonium tetrakis(pentafluorophenyl) borate,

tri(sec-butyl)ammonium tetrakis(pentafluorophenyl) borate,

N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate,

N,N-dimethylanilinium n-butyltris(pentafluorophenyl) borate,

N,N-dimethylanilinium benzyltris(pentafluorophenyl) borate,

N,N-dimethylanilinium tetrakis(4-(t-butyldimethylsilyl)-2, 3, 5,6-tetrafluorophenyl) borate,

N,N-dimethylanilinium tetrakis(4-(triisopropylsilyl)-2, 3, 5,6-tetrafluorophenyl) borate,

N,N-dimethylanilinium pentafluorophenoxytris(pentafluorophenyl) borate,

N,N-diethylanilinium tetrakis(pentafluorophenyl) borate,

N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl)borate,

dimethyltetradecylammonium tetrakis(pentafluorophenyl) borate,

dimethylhexadecylammonium tetrakis(pentafluorophenyl) borate,

dimethyloctadecylammonium tetrakis(pentafluorophenyl) borate,

methylditetradecylammonium tetrakis(pentafluorophenyl) borate,

methylditetradecylammonium (hydroxyphenyl)tris(pentafluorophenyl)borate,

methylditetradecylammonium(diethylaluminoxyphenyl)tris(pentafluorophenyl) borate,

methyldihexadecylammonium tetrakis(pentafluorophenyl) borate,

methyldihexadecylammonium (hydroxyphenyl)tris(pentafluorophenyl) borate,

methyldihexadecylammonium(diethylaluminoxyphenyl)tris(pentafluorophenyl) borate,

methyldioctadecylammonium tetrakis(pentafluorophenyl) borate,

methyldioctadecylammonium (hydroxyphenyl)tris(pentafluorophenyl) borate,

methyldioctadecylammonium(diethylaluminoxyphenyl)tris(pentafluorophenyl) borate,

methyldioctadecylammonium tetrakis(pentafluorophenyl) borate,

phenyldioctadecylammonium tetrakis(pentafluorophenyl) borate,

phenyldioctadecylammonium (hydroxyphenyl)tris(pentafluorophenyl) borate,

phenyldioctadecylammonium(diethylaluminoxyphenyl)tris(pentafluorophenyl) borate,

(2,4,6-trimethylphenyl)dioctadecylammonium tetrakis(pentafluorophenyl)borate,

(2,4,6-trimethylphenyl)dioctadecylammonium(hydroxyphenyl)tris(pentafluorophenyl)-borate,

(2,4,6-timethylphenyl)dioctadecylammonium (diethylaluminoxypheny)

tris(pentafluorophenyl)borate,

(2,4,6-trifluorophenyl)dioctadecylammoniumtetrakis(pentafluorophenyl)borate,

(2,4,6-trifluorophenyl)dioctadecylammonium(hydroxyphenyl)tris(pentafluorophenyl)-borate,

(2,4,6-trifluorophenyl)dioctadecylammonium(diethylaluminoxyphenyl)tris(pentafluoro-phenyl) borate,

(pentafluorophenyl)dioctadecylammoniumtetrakis(pentafluorophenyl)borate,

(pentafluorophenyl)dioctadecylammonium(hydroxyphenyl)tris(pentafluorophenyl)-borate,

(pentafluorophenyl)dioctadecylammonium(diethylaluminoxyphenyl)tris(pentafluoro-phenyl) borate,

(p-trifluoromethylphenyl)dioctadecylammoniumtetrakis(pentafluorophenyl)borate,

(p-trifluoromethylphenyl)dioctadecylammonium(hydroxyphenyl)tris(pentafluoro-phenyl) borate,

(p-trifluoromethylphenyl)dioctadecylammonium(diethylaluminoxyphenyl)tris(pentafluorophenyl) borate,

p-nitrophenyldioctadecylammonium tetrakis(pentafluorophenyl)borate,

p-nitrophenyldioctadecylammonium (hydroxyphenyl)tris(pentafluorophenyl)borate,

p-nitrophenyldioctadecylammonium(diethylaluminoxyphenyl)tris(pentafluorophenyl) borate, and mixtures ofthe foregoing,

dialkyl ammonium salts such as:

di-(i-propyl)ammonium tetrakis(pentafluorophenyl) borate,methyloctadecylammonium tetrakis(pentafluorophenyl) borate,methyloctadodecylammonium tetrakis(pentafluorophenyl) borate, anddioctadecylammonium tetrakis(pentafluorophenyl) borate;

tri-substituted phosphonium salts such as:

triphenylphosphonium tetrakis(pentafluorophenyl) borate,methyldioctadecylphosphonium tetrakis(pentafluorophenyl) borate, andtri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl) borate;

di-substituted oxonium salts such as:

diphenyloxonium tetrakis(pentafluorophenyl) borate, di(o-tolyl)oxoniumtetrakis(pentafluorophenyl) borate, and di(octadecyl)oxoniumtetrakis(pentafluorophenyl) borate;

di-substituted sulfonium salts such as:

di(o-tolyl)sulfonium tetrakis(pentafluorophenyl) borate, andmethylcotadecylsulfonium tetrakis(pentafluorophenyl) borate.

Preferred trialkylammonium cations are methyldioctadecylammonium anddimethyloctadecylammonium. The use of the above Bronsted acid salts asactivating cocatalysts for addition polymerization catalysts is known inthe art, having been disclosed in U.S. Pat. Nos. 5,064,802, 5,919,983,5,783,512 and elsewhere. Preferred dialkylarylammonium cations arefluorophenyldioctadecylammonium-, perfluoro-phenyldioctacecylammonium-and p-trifluoromethylphenyldi(octadecyl)ammonium cations. It should benoted that certain of the cocatalysts, especially those containing ahydroxyphenyl ligand in the borate anion, may require the addition of aLewis acid, especially a trialkylaluminum compound, to thepolymerization mixture or the catalyst composition, in order to form theactive catalyst composition.

Another suitable ion forming, activating cocatalyst comprises a salt ofa cationic oxidizing agent and a noncoordinating, compatible anionrepresented by the formula:

(Ox^(e+))_(d)(A^(d−))_(e).

wherein:

Ox^(e+) is a cationic oxidizing agent having a charge of e⁺;

e is an integer from 1 to 3; and

A^(d−) and d are as previously defined.

Examples of cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag⁺ or Pb⁺². Preferred embodimentsof A^(d−) are those anions previously defined with respect to theBronsted acid containing activating cocatalysts, especiallytetrakis(pentafluorophenyl)borate. The use of the above salts asactivating cocatalysts for addition polymerization catalysts is known inthe art, having been disclosed in U.S. Pat. No. 5,321,106.

Another suitable ion forming, activating cocatalyst comprises a compoundwhich is a salt of a carbenium ion and a noncoordinating, compatibleanion represented by the formula:

Ĉ⁺ A⁻

wherein:

Ĉ⁺ is a C₁₋₂₀ carbenium ion; and

A is as previously defined. A preferred carbenium ion is the tritylcation, that is triphenylmethylium. The use of the above carbenium saltsas activating cocatalysts for addition polymerization catalysts is knownin the art, having been disclosed in U.S. Pat. No. 5,350,723.

A further suitable ion forming, activating cocatalyst comprises acompound which is a salt of a silylium ion and a noncoordinating,compatible anion represented by the formula:

R³ ₃Si(X′)_(q)+A⁻

wherein:

R³ is C₁₋₁₀ hydrocarbyl, and X′, q and A⁻ are as previously defined.

Preferred silylium salt activating cocatalysts are trimethylsilyliumtetrakispentafluorophenylborate, triethylsilyliumtetrakispentafluorophenylborate and ether substituted adducts thereof.The use of the above silylium salts as activating cocatalysts foraddition polymerization catalysts is known in the art, having beendisclosed in U.S. Pat. No. 5,625,087.

Certain complexes of alcohols, mercaptans, silanols, and oximes withtris(pentafluorophenyl)borane are also effective catalyst activators andmay be used according to the present invention. Such cocatalysts aredisclosed in U.S. Pat. No. 5,296,433.

Another class of suitable catalyst activators are expanded anioniccompounds corresponding to the formula: (A^(1+a) ¹ )_(b)¹(Z¹J¹j¹)^(−c1)d¹,

wherein:

A¹ is a cation of charge +a¹,

Z¹ is an anion group of from 1 to 50, preferably 1 to 30 atoms, notcounting hydrogen atoms, further containing two or more Lewis basesites;

J¹ independently each occurrence is a Lewis acid coordinated to at leastone Lewis base site of Z¹, and optionally two or more such J¹ groups maybe joined together in a moiety having multiple Lewis acidicfunctionality,

j¹ is a number from 2 to 12 and

a¹, b¹, c¹, and d¹ are integers from 1 to 3, with the proviso that a¹×b¹is equal to c¹×d¹.

The foregoing cocatalysts (illustrated by those having imidazolide,substituted imidazolide, imidazolinide, substituted imidazolinide,benzimidazolide, or substituted benzimidazolide anions) may be depictedschematically as follows:

wherein:

A¹⁺ is a monovalent cation as previously defined, and preferably is atrihydrocarbyl ammonium cation, containing one or two C₁₀₋₄₀ alkylgroups, especially the methylbis(tetradecyl)ammonium- ormethylbis(octadecyl)ammonium-cation,

R⁸, independently each occurrence, is hydrogen or a halo, hydrocarbyl,halocarbyl, halohydrocarbyl, silylhydrocarbyl, or silyl, (includingmono-, di- and tri(hydrocarbyl)silyl) group of up to 30 atoms notcounting hydrogen, preferably C₁₋₂₀ alkyl, and

J¹ is tris(pentafluorophenyl)borane or tris(pentafluorophenyl)aluminane.

Examples of these catalyst activators include thetrihydrocarbylammonium-, especially, methylbis(tetradecyl)ammonium- ormethylbis(octadecyl)ammonium-salts of:

bis(tris(pentafluorophenyl)borane)imidazolide,

bis(tris(pentafluorophenyl)borane)-2-undecylimidazolide,bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolide,bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolide,

bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolide,

bis(tris(pentafluorophenyl)borane)imidazolinide,

bis(tris(pentafluorophenyl)borane)-2-undecylimidazolinide,

bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolinide,

bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolinide,

bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolinide,

bis(tris(pentafluorophenyl)borane)-5,6-dimethylbenzimidazolide,

bis(tris(pentafluorophenyl)borane)-5,6-bis(undecyl)benzimidazolide,

bis(tris(pentafluorophenyl)alumane)imidazolide,

bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolide,

bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolide,

bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolide,

bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolide,

bis(tris(pentafluorophenyl)alumane)imidazolinide,

bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolinide,

bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolinide,

bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolinide,

bis(tris(pentafluorophenyl)alumane)-2-unhepatdecylimidazolinide,

bis(tris(pentafluorophenyl)alumane)-5,6-dimethylbenzimidazolide, and

bis(tris(pentafluorophenyl)alumane)-5,6-bis(undecyl)benzimidazolide.

A further class of suitable activating cocatalysts include cationicGroup 13 salts corresponding to the formula:

[M″Q¹ ₂L′_(1′),]⁺ (Ar^(f) ₃M′Q²)⁻

wherein:

M″ is aluminum, gallium, or indium;

M′ is boron or aluminum;

Q¹ is C₁₋₂₀ hydrocarbyl, optionally substituted with one or more groupswhich independently each occurrence are hydrocarbyloxy,hydrocarbylsiloxy, hydrocarbylsilylamino, di(hydrocarbylsilyl)amino,hydrocarbylamino, di(hydrocarbyl)amino, di(hydrocarbyl)phosphino, orhydrocarbylsulfido groups having from 1 to 20 atoms other than hydrogen,or, optionally, two or more Q¹ groups may be covalently linked with eachother to form one or more fused rings or ring systems;

Q² is an alkyl group, optionally substituted with one or more cycloalkylor aryl groups, said Q² having from 1 to 30 carbons;

L′ is a monodentate or polydentate Lewis base, preferably L′ isreversibly coordinated to the metal complex such that it may bedisplaced by an olefin monomer, more preferably L′ is a monodentateLewis base;

l′ is a number greater than zero indicating the number of Lewis basemoieties, L′, and

Ar^(f) independently each occurrence is an anionic ligand group;preferably Ar^(f) is selected from the group consisting of halide, C₁₋₂₀halohydrocarbyl, and Q¹ ligand groups, more preferably Ar^(f) is afluorinated hydrocarbyl moiety of from 1 to 30 carbon atoms, mostpreferably Ar^(f) is a fluorinated aromatic hydrocarbyl moiety of from 6to 30 carbon atoms, and most highly preferably Ar^(f) is aperfluorinated aromatic hydrocarbyl moiety of from 6 to 30 carbon atoms.

Examples of the foregoing Group 13 metal salts are alumiciniumtris(fluoroaryl)borates or gallicinium tris(fluoroaryl)boratescorresponding to the formula: [M″Q¹ ₂L′_(r),]⁺ (Ar^(f) ₃BQ²)⁻, whereinM″ is aluminum or gallium; Q¹ is C₁₋₂₀ hydrocarbyl, preferably C₁₋₈alkyl; Ar^(f) is perfluoroaryl, preferably pentafluorophenyl; and Q² isC₁₋₈ alkyl, preferably C₁₋₈ alkyl. More preferably, Q¹ and Q² areidentical C₁₋₈ alkyl groups, most preferably, methyl, ethyl or octyl.

The foregoing activating cocatalysts may also be used in combination. Anespecially preferred combination is a mixture of atri(hydrocarbyl)aluminum or tri(hydrocarbyl)borane compound having from1 to 4 carbons in each hydrocarbyl group or an ammonium borate with anoligomeric or polymeric alumoxane compound.

The molar ratio of catalyst/cocatalyst employed preferably ranges from1:10,000 to 100:1, more preferably from 1:5000 to 10:1, most preferablyfrom 1:1000 to 1:1. Alumoxane, when used by itself as an activatingcocatalyst, is employed in large quantity, generally at least 100 timesthe quantity of metal complex on a molar basis.Tris(pentafluorophenyl)borane, where used as an activating cocatalyst isemployed in a molar ratio to the metal complex of form 0.5:1 to 10:1,more preferably from 1:1 to 6:1 most preferably from 1:1 to 5:1. Theremaining activating cocatalysts are generally employed in approximatelyequimolar quantity with the metal complex.

The catalysts, whether or not supported in any suitable manner, may beused to polymerize ethylenically unsaturated monomers having from 2 to100,000 carbon atoms either alone or in combination. Preferred additionpolymerizable monomers for use herein include olefins, diolefins andmixtures thereof. Preferred olefins are aliphatic or aromatic compoundscontaining vinylic unsaturation as well as cyclic compounds containingethylenic unsaturation. Examples of the latter include cyclobutene,cyclopentene, norbornene, and norbornene derivatives that aresubstituted in the 5- and 6-positions with C₁₋₂₀ hydrocarbyl groups.Preferred diolefins are C₄₋₄₀ diolefins compounds, including ethylidenenorbornene, 1,4-hexadiene, norbornadiene, and the like. The catalystsand processes herein are especially suited for use in preparation ofethylene/1-butene, ethylene/1-hexene, ethylene/styrene,ethylene/propylene, ethylene/1-pentene, ethylene/4-methyl-1-pentene andethylene/1-octene copolymers as well as terpolymers of ethylene,propylene and a nonconjugated diene, such as, for example, EPDMterpolymers.

Most preferred monomers include the C₂₋₂₀ α-olefins, especiallyethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene,3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, long chainmacromolecular α-olefins, and mixtures thereof. Other preferred monomersinclude styrene, C₁₋₄ alkyl substituted styrene, ethylidenenorbornene,1,4-hexadiene, 1,7-octadiene, vinylcyclohexane, 4-vinylcyclohexene,divinylbenzene, and mixtures thereof with ethylene. Long chainmacromolecular α-olefins are vinyl terminated polymeric remnants formedin situ during continuous solution polymerization reactions. Undersuitable processing conditions such long chain macromolecular units arereadily polymerized into the polymer product along with ethylene andother short chain olefin monomers to give small quantities of long chainbranching in the resulting polymer.

Preferred monomers include a combination of ethylene and one or morecomonomers selected from monovinyl aromatic monomers,4-vinylcyclohexene, vinylcyclohexane, norbornadiene,ethylidene-norbornene, C₃₋₁₀ aliphatic α-olefins (especially propylene,isobutylene, 1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene,and 1-octene), and C₄₋₄₀ dienes. Most preferred monomers are mixtures ofethylene and styrene; mixtures of ethylene, propylene and styrene;mixtures of ethylene, styrene and a nonconjugated diene, especiallyethylidenenorbornene or 1,4-hexadiene, and mixtures of ethylene,propylene and a nonconjugated diene, especially ethylidenenorbornene or1,4-hexadiene.

In general, the polymerization may be accomplished at conditions wellknown in the prior art for Ziegler-Natta or Kaminsky-Sinn typepolymerization reactions, that is, temperatures from 0-250° C.,preferably 30 to 200° C. and pressures from atmospheric to 10,000atmospheres. Suspension, solution, slurry, gas phase, solid state powderpolymerization or other process condition may be employed if desired. Asupport, especially silica, alumina, or a polymer (especiallypoly(tetrafluoroethylene) or a polyolefin) may be employed, anddesirably is employed when the catalysts are used in a gas phasepolymerization process. The support is preferably employed in an amountto provide a weight ratio of catalyst (based on metal):support from1:10⁶ to 1:10³, more preferably from 1:10⁶ to 1:10⁴.

In most polymerization reactions the molar ratio ofcatalyst:polymerizable compounds employed is from 10^(−12:)1 to 10⁻¹:1,more preferably from 10⁻⁹:1 to 10⁻⁵:1.

Suitable solvents use for solution polymerization are liquids that aresubstantially inert under process conditions encountered in their usage.Examples include straight and branched-chain hydrocarbons such asisobutane, butane, pentane, hexane, heptane, octane, and mixturesthereof; cyclic and alicyclic hydrocarbons such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof; perfluorinated hydrocarbons such as perfluorinated C₄₋₁₀alkanes, and alkyl-substituted aromatic compounds such as benzene,toluene, xylene, and ethylbenzene. Suitable solvents also include liquidolefins which may act as monomers or comonomers.

The catalysts may be utilized in combination with at least oneadditional homogeneous or heterogeneous polymerization catalyst in thesame reactor or in separate reactors connected in series or in parallelto prepare polymer blends having desirable properties. An example ofsuch a process is disclosed in WO 94/00500.

The catalysts of the present invention are particularly advantageous forthe production of ethylene homopolymers and ethylene/α-olefin copolymershaving high levels of long chain branching. The use of the catalysts ofthe present invention in continuous polymerization processes, especiallycontinuous, solution polymerization processes, allows for elevatedreactor temperatures which favor the formation of vinyl terminatedpolymer chains that may be incorporated into a growing polymer, therebygiving a long chain branch. The use of the present catalyst compositionsadvantageously allows for the economical production of ethylene/α-olefincopolymers having processability similar to high pressure, free radicalproduced low density polyethylene.

The present catalyst compositions may be advantageously employed toprepare olefin polymers having improved processing properties bypolymerizing ethylene alone or ethylene/α-olefin mixtures with lowlevels of a “H” branch inducing diene, such as norbornadiene,1,7-octadiene, or 1,9-decadiene. The unique combination of elevatedreactor temperatures, high molecular weight (or low melt indices) athigh reactor temperatures and high comonomer reactivity advantageouslyallows for the economical production of polymers having excellentphysical properties and processability. Preferably such polymerscomprise ethylene, a C₃₋₂₀ α-olefin and a “H”-branching comonomer.Preferably, such polymers are produced in a solution process, mostpreferably a continuous solution process.

The catalyst composition may be prepared as a homogeneous catalyst byaddition of the requisite components to a solvent or diluent in whichpolymerization will be conducted. The catalyst composition may also beprepared and employed as a heterogeneous catalyst by adsorbing,depositing or chemically attaching the requisite components on aninorganic or organic particulated solid. Examples of such solidsinclude, silica, silica gel, alumina, clays, expanded clays (aerogels),aluminosilicates, trialkylaluminum compounds, and organic or inorganicpolymeric materials, especially polyolefins. In a preferred embodiment,a heterogeneous catalyst is prepared by reacting an inorganic compound,preferably a tri(C₁₋₄ alkyl)aluminum compound, with an activatingcocatalyst, especially an ammonium salt of ahydroxyaryl(trispentafluorophenyl)borate, such as an ammonium salt of(4-hydroxy-3,5-ditertiarybutylphenyl)tris(pentafluorophenyl)borate or(4-hydroxyphenyl)tris(pentafluorophenyl)borate. This activatingcocatalyst is deposited onto the support by coprecipitating, imbibing,spraying, or similar technique, and thereafter removing any solvent ordiluent. The metal complex is added to the support, also by adsorbing,depositing or chemically attaching the same to the support, eithersubsequently, simultaneously or prior to addition of the activatingcocatalyst.

When prepared in heterogeneous or supported form, the catalystcomposition is employed in a slurry or gas phase polymerization. As apractical limitation, slurry polymerization takes place in liquiddiluents in which the polymer product is substantially insoluble.Preferably, the diluent for slurry polymerization is one or morehydrocarbons with less than 5 carbon atoms. If desired, saturatedhydrocarbons such as ethane, propane or butane may be used in whole orpart as the diluent. Likewise, the α-olefin monomer or a mixture ofdifferent α-olefin monomers may be used in whole or part as the diluent.Most preferably, at least a major part of the diluent comprises the(x-olefin monomer or monomers to be polymerized. A dispersant,particularly an elastomer, may be dissolved in the diluent utilizingtechniques known in the art, if desired.

At all times, the individual ingredients as well as the recoveredcatalyst components must be protected from oxygen and moisture.Therefore, the catalyst components and catalysts must be prepared andrecovered in an oxygen and moisture free atmosphere. Preferably,therefore, the reactions are performed in the presence of an dry, inertgas, such as, for example, nitrogen.

The polymerization may be carried out as a batchwise or a continuouspolymerization process. A continuous process is preferred, in whichevent catalyst, ethylene, comonomer, and optionally solvent, arecontinuously supplied to the reaction zone, and polymer productcontinuously removed therefrom.

Without limiting in any way the scope of the invention, one means forcarrying out such a polymerization process is as follows: In astirred-tank reactor, the monomers to be polymerized are introducedcontinuously, together with solvent and an optional chain transferagent. The reactor contains a liquid phase composed substantially ofmonomers, together with any solvent or additional diluent and dissolvedpolymer. If desired, a small amount of a “H”-branch inducing diene suchas norbornadiene, 1,7-octadiene or 1,9-decadiene may also be added.Catalyst and cocatalyst are continuously introduced in the reactorliquid phase. The reactor temperature and pressure may be controlled byadjusting the solvent/monomer ratio, the catalyst addition rate, as wellas by cooling or heating coils, jackets or both. The polymerization rateis controlled by the rate of catalyst addition. The ethylene content ofthe polymer product is determined by the ratio of ethylene to comonomerin the reactor, which is controlled by manipulating the respective feedrates of these components to the reactor. The polymer product molecularweight is controlled, optionally, by controlling other polymerizationvariables such as the temperature, monomer concentration, or by thepreviously mention chain transfer agent, such as a stream of hydrogenintroduced to the reactor, as is well known in the art. The reactoreffluent is contacted with a catalyst kill agent such as water. Thepolymer solution is optionally heated, and the polymer product isrecovered by flashing off gaseous monomers as well as residual solventor diluent at reduced pressure, and, if necessary, conducting furtherdevolatilization in equipment such as a devolatilizing extruder. In acontinuous process the mean residence time of the catalyst and polymerin the reactor generally is from about 5 minutes to 8 hours, andpreferably from 10 minutes to 6 hours.

Ethylene homopolymers and ethylene/α-olefin copolymers are particularlysuited for preparation according to the invention. Generally suchpolymers have densities from 0.85 to 0.96 g/ml. Typically the molarratio of α-olefin comonomer to ethylene used in the polymerization maybe varied in order to adjust the density of the resulting polymer. Whenproducing materials with a density range of from 0.91 to 0.93 thecomonomer to monomer ratio is less than 0.2, preferably less than 0.05,even more preferably less than 0.02, and may even be less than 0.01. Inthe above polymerization process hydrogen has been found to effectivelycontrol the molecular weight of the resulting polymer. Typically, themolar ratio of hydrogen to monomer is less than about 0.5, preferablyless than 0.2, more preferably less than 0.05, even more preferably lessthan 0.02 and may even be less than 0.01.

EXAMPLES

It is understood that the present invention is operable in the absenceof any component which has not been specifically disclosed. Thefollowing examples are provided in order to further illustrate theinvention and are not to be construed as limiting. Unless stated to thecontrary, all parts and percentages are expressed on a weight basis. Theterm “overnight”, if used, refers to a time of approximately 16-18hours, “room temperature”, if used, refers to a temperature of about20-25° C., and “mixed alkanes” refers to a mixture of hydrogenatedpropylene oligomers, mostly C₆-C₁₂ isoalkanes, available commerciallyunder the trademark Isopar E™ from Exxon Chemicals Inc.

All solvents were purified using the technique disclosed by Pangborn etal, Organometallics, 15, 1518-1520, (1996). ¹H and ¹³C NMR shifts werereferenced to internal solvent resonances and are reported relative toTMS.

Example 1 1,8-dihydro-3-hydoxy-dibenzo[e,h]azulene (keto isomer)

(A) Preparation of10-(trimethylsilyl)ethynyl-5H-dibenzo[a,d]cycloheptene

To a stirred mixture of 10-bromo-5H-dibenzo[a,d]cycloheptene (9.70 g,0.036 mol) (J. Med. Chem. 1995 38(4), 708-714), palladium(II)chloridebistriphenylphosphine (1.25 g, 0.018 mol), triphenyl phosphine (0.942 g,0.0036 mol), copper(ll)acetate hydrate (0.327 g, 0.002 mol) in 20 ml ofdiisopropyl amine was added (trimethylsilyl)acetylene (3.88 g, 0.040mol) and refluxed for an hour. The resulting mixture was concentrated,diluted with hexane (25 ml) and filtered through a pad of silica gel.The filtrate was concentrated to yield 5.57 g of10-(trimethylsilyl)ethynyl-5H-dibenzo[a,d]cycloheptene.

(B) Preparation of 1,8-dihydro-3-hydoxy-dibenzo[e,h]azulene

A mixture of 10-(trimethylsilyl)ethynyl-5H-dibenzo[a,d]cycloheptene(5.57 g, 0.020 mol), triethyl amine(3.89 g, 0.039 mol), water (3.45 g,0.385 mol), tristriphenyl phosphine rhodium chloride (0.178 g, 0.002mol) and triphenyl phosphine (2.52 g, 0.010 mol) in 70 ml of THF waspressurized in a Parr reactor with carbon monoxide to 800 psi (690 kPa)and stirred and heated to 160C for 10 hr. The product,1,8-dihydro-3-hydoxy-dibenzo[e,h]azulene, was isolated by concentratingthe reaction and chromatography of the residue over silica gel withmethlyene chloride as eluant to give 3.39 g of yellow oil.

¹H NMR (C₆D₆, 300 MHz; δ (ppm): 2.8 (m), 3.0 (br,d), 3.45 (b,d), 3.6(br,d), 3.85 (br,d), 7,35 (m), 7.43 (m), 7.60(d,6.5 Hz), 7.91(d,6.5 Hz).

¹³C NMR (C₆D₆, 75.45 MHz; δ (ppm)): 28.1, 34.7, 41.2, 125.8, 126.1,127.3, 128.2, 128.9, 129.5, 131.2, 133.9, 138.9, 140.3, 167.5, 207.1

IR: C═O 1697 cm⁻¹

Example 2 1,8-dihydro-dibenzo[e,h]azulene

To a stirred solution of 1,8-dihydro-3hydoxy-dibenzo[e,h]azulene (3.30g, 0.013 mol) in 50 ml of chloroform and 5 ml of ethanol was added 0.500g (0.013 mol) of sodium borohydride and allowed to stir for 12 hr. Thereaction was worked up by adding 5 ml of a 10 weight percent, aqueousHCl solution and extracting with methylene chloride. The organic layerwas dried and concentrated and chromatographed over silica gel to yield1.65 g of a white solid. The proton NMR and the mass spectrum of thismaterial is consistent with the desired product,1,8dihydro-dibenzo[,h]azulene.

¹NMR (C₆D₆, 300 MHz; δ (ppm): 3.7 (br,s), 6.6 (d,5 Hz), 7.04 (d, 5 Hz),7.2-7.35 (m), 7.52 (d, 7 Hz)

¹³C NMR (C₆D₆, 75.45 MHz; δ (ppm)): 41.9, 43.8, 126, 126.1, 126.3,126.7, 127.8, 128.0, 132.5, 133.7, 134.7, 137.8, 137.9, 141.9, 142.1

MS (m/z): 230 (M+), 215, 202

Example 3(2,8-dihydrodibenzo[e,h]azulen-2)-N-(1,1-dimethylethyl)dimethyl-silanamine

To 1,8-dihydro-dibenzo[e,h]azulene (0.461 g, 2.00 mmol) in 40 mL THF wasadded 2.5 M butyl lithium (0.88 mL, 2.2 mmol). The solution turned fromclear colorless to dark orange immediately. After 0.5 hr. this solutionwas added slowly to dimethyl dichlorosilane (2.4 mL, 20 mmol) to give apale yellow solution. Volatile materials were removed under reducedpressure. The residue was redisolved in THF and tert-butylamine (0.46mL, 4.4 mmol) was added. A pearlescent precipitated formed within aminute. After stirring over night the volatile materials were removedunder reduced pressure. The residue was extracted three times with atotal of 90 mL hexanes. The extracts were filtered and volatilematerials were removed from the combined filtrates under reducedpressure to give 0.716 g of a thick yellow liquid. The NMR spectra areconsistent with a mixture of (2,8-dihydrodibenzo[e,h]azulen-2)-N-(1,1-dimethylethyl)dimethylsilanamine and a positionalisomer(2,8-dihydrodibenzo-[e,h]azulen-1)-N-(1,1-dimethylethyl)dimethylsilanamine,as well as double bond isomers of each.

¹NMR (C₆D₆, 300 MHz; δ (ppm)): −0.12 (s); −0.05 (s); 0.35 (s); 0.46 (brs); 0.62 (br s); 0.94 (s); 1.11 (s); 1.13-1.21 (m); 3.51-3.85 (m); 4.18(s); 6.61 (d, 5 Hz); 6.96-7.22 (m); 7.38 (m); 7.47 (d, 7 Hz); 7.54 (m).

¹³C NMR (C₆D₆, 75.45 MHz; δ (ppm)): 0.5, 0.8, 1.8, 14.3, 33.7, 33.9,42.3, 43.9, 47.7, 49.4, 49.6, 55.4, 126.1, 126.4, 126.5, 126.8, 127.1,127.3, 127.6, 128.1, 128.2, 128.5, 128.8, 133.8, 134.2, 135.0, 135.2,135.4, 138.2, 138.3, 138.5, 138.7, 141.1, 143.3, 143.8, 144.6, 146.7,148.9.

Example 4

(2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidetitanium dichloride

The mixture from example 3 (0.716 g, 1.99 mmol) was dissolved in 40 mLn-octane and titanium tetrakis(dimethylamide) (0.446 g, 1.99 mmol) wasadded. The solution was heated to and stirred at reflux for 2 days. Thesolution turned dark red. A small aliquot of the cooled solution wasremoved and volatile components of this aliquot were removed underreduced pressure. The NMR spectra of the residue are consistent with(2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidetitanium bis(dimethylamide). Volatile materials were removed from thebulk solution under reduced pressure. The residue was dissolved inhexanes. A solution of 1.0 M boron trichloride in hexanes (4.0 mL, 4.0mmol) was added to this solution. A precipitate formed immediately.After one hour the yellow solid was collected by vacuum filtration. Thesolids were washed once with hexanes. Removal of volatiles under reducedpressure gave 0.655 g of material. NMR spectra are consistent with avery pure sample of(2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidetitanium dichloride.

¹NMR (C₆D₆, 300 MHz; δ (ppm)): 0.36 (S, 6H); 1.39 (s, 9H); 3.61 (d, 13.8Hz, 1H); 4.48 (d, 13.8 Hz, 1H); 6.68 (s, 2H O; 7.02-7.16 (m, 6H); 7.43(d, 6.6 Hz, 2H).

¹³C NMR (C₆D₆, 75.45 MHz; δ (ppm)): −0.39, 32.4, 42.6, 64.1, 110.4,123.9, 126.7, 129.1, 129.5, 130.0, 132.7, 139.7, 140.4.

Example 5(2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidedimethyltitanium

To a slurry of(2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidetitanium dichloride (0.460 g, 0.966 mmol) in diethylether was added 3.0M methyl magnesium chloride in THF (0.97 mL, 2.9 mmol). The colorchanged immediately. After stirring the mixture overnight the volatileswere removed under reduced pressure. The residue was extracted threetimes with a total of 90 mL hexanes. The hexanes extracts were filteredand the volatiles were removed from the combined filtrate under reducedpressure to give 0.293 g of a yellow solid. The nmr spectra areconsistent with the desired compound,(2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidedimethyltitanium.

¹NMR (C₆D₆, 300 MHz; δ (ppm)): 0.39 (s, 6H); 0.60 (s, 6H); 1.54 (s, 9H);3.57 (d, 13.8 Hz, 1H); 4.00 (d, 13.8 Hz, 1H); 6.31 (s, 2H); 7.08-7.2 (m,6H); 7.59 (m, 2H).

¹³C NMR (C₆D₆, 75.45 MHz; δ (ppm)): 0.74, 34.2, 42.5, 54.8, 59.7, 106.0,119.9, 127.0, 128.6, 129.1, 129.2, 138.4, 134.1, 135.2.

Polymerization General Conditions

Mixed alkanes and liquid olefins are purified by sparging with purifiednitrogen followed by passage through columns containing alumina (A-2,available from LaRoche Inc.) and Q5 reactant (available from EnglehardChemicals Inc.) at 50 psig using a purified nitrogen pad. All transfersof solvents and solutions described below are accomplished using agaseous pad of dry, purified nitrogen or argon. Gaseous feeds to thereactor are purified by passage through columns of A-204 alumina(available from LaRoche Inc.) and Q5 reactant. The aluminas arepreviously activated by treatment at 375° C. with nitrogen, and Q5reactant is activated by treatment at 200° C. with 5 percent hydrogen innitrogen.

Polymerization 1

A stirred, two-liter Parr reactor was charged with approximately 433 gof toluene and 455 g of styrene comonomer. Hydrogen was added as amolecular weight control agent by differential pressure expansion from a75 mL addition tank at 50 psig (345 kPa). The reactor was heated to 90°C. and saturated with ethylene at 200 psig (1.4 MPa). The appropriateamount of catalyst,(2,8-dihydrodibenzo-[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)-dimethylsilanamidedimethyltitanium (Example 5), and cocatalyst as 0.005M solutions intoluene were premixed in a glovebox and transferred to a catalystaddition tank and injected into the reactor. (Periodic additions ofcatalyst/cocatalyst solution may be added during the course of the run.)The polymerization conditions were maintained during the run withethylene on demand.

The resulting solution was removed from the reactor into a nitrogenpurged collection vessel containing 100 ml of isopropyl alcohol and 20ml of a 10 weight percent toluene solution of hindered phenolantioxidant (Irganox™ 1010 from Ciba Geigy Corporation) and phosphorusstabilizer (Irgafos™ 168 from Ciba Geigy Corporation). Polymers formedare dried in a programmed vacuum oven with a maximum temperature of 140°C. and a 20 hour heating period. The results are contained in Table 1.

Polymerization 2

Runs 3 and 4 were performed using a 1 gallon stirred autoclave reactor.The reactor was charged with 1200 mL toluene and 400 mL styrene (run 3)or 600 mL toluene and 1000 mL styrene (run 4) then heated to the desiredtemperature and saturated with ethylene (1.9 MPa, 275 psig for run 3,1.0 MPa, 150 psig for run 4). The catalyst was prepared in a drybox bymixing together the metal complex (Example 5) and cocatalyst (a mixtureof dioctadecylphenylammonium tetrakispentafluorophenylborate (DPTPB) andisobutylaluminum modified methylalumoxane (Akzo Nobel MMAO-3A, 40 μmoland 70 μmol for runs 3 and 4 respectively). Additional solvent was thenadded to give a total volume of 13 mL.

DPTPB was prepared in the following manner. N,N-dioctadecylaniline (0.15g, 0.25 mMol; obtained from the Sigma-Aldrich Library of Rare Chemicals)was placed into a four ounce bottle with a magnetic stir bar.Methylcyclohexane (25 mL) was added to dissolve the amine, followed by0.125 mL of 2M HCl. The mixture was stirred vigorously for 30 minutes,then a solution of LiB(C₆F₅)₄.Et₂O (0.191 g, 0.25 mMol; obtained fromthe Boulder Scientific Company) in 20 mL of water was added. The mixturewas stirred for two hours. At the end of this time, a two-phase mixturewas obtained; the upper (organic) layer was pale green in color. Themixture was transferred to a separatory funnel, and 30 mL of a 30 weightpercent solution of NaCl in water was added. The funnel was shaken,allowed to settle, and the aqueous layer was removed and discarded. Theseparation was repeated with an additional 30 mL of 30 percent NaCl inwater and with 30 mL of water; in each case, the aqueous layer wasdiscarded. The organic layer that remained was dried over MgSO₄ for onehour, filtered, transferred to a bottle, sparged thoroughly with N₂, andbrought into the drybox. The solution was transferred to a weighed jar,and the volatile materials were removed under vacuum. A pale green oil(0.23 g) remained. This material was dissolved in 25 mL of toluene toprepare a 0.0072M solution.

The catalyst solution was then transferred by syringe to a catalystaddition loop and injected into the reactor over approximately 1-2minutes using a flow of high pressure solvent (toluene). Thepolymerization was allowed to proceed for 10 minutes while feedingethylene on demand to maintain the reactor pressure. The amount ofethylene consumed during the reaction was monitored using a mass flowmeter. The polymer solution was expelled from the reactor into anitrogen-purged glass container containing 200 mL of isopropanol.Approximately 20 ml of a 10 weight percent toluene solution of hinderedphenol antioxidant (Irganox™ 1010 from Ciba Geigy Corporation) andphosphorus stabilizer (Irgafos™ 168 from Ciba Geigy Corporation addedand the solution stirred. The polymer solution was expelled into a tray,air dried overnight, then thoroughly dried in a vacuum oven for severaldays. Results are contained in Table 1.

TABLE 1 Cat. Cocatalyst Time T. Yield Run (μmol) (μmol) (min) (° C.) (g)eff.⁴ [Styrene]⁵ Mw 1 3 TPFB¹ (9) 30  90 110 0.77 32.2 — 2 5 DMTPB² (3)66  90 105 0.44 30.5 — 3 4 DATPB³ (4.8) 10 115 100 0.52 12.6 232,000 4 7DPTPB³ (8.4) 10  90 146 0.43 35.6 120,000 ¹trispentafluorophenylborane²dioctadecylmethylammonium tetrakispentafluorophenylborate³dioctadecylphenylammonium tetrakispentafluorophenylborate (+MMAO-3A)⁴efficiency, g polymer/μg Ti ⁵polymerized styrene content of polymer,mol percent

What is claimed is:
 1. A polycyclic, fused ring compound correspondingto the formula: (Cp*)_(p)-M*(I) orCpM(Z)_(z)(X)_(x)(L)_(l)(X′)_(x)  (II), where Cp* is a polycyclic, fusedring ligand or inertly substituted derivative thereof comprising atleast: (1) a cyclopentadienyl ring, (2) a 6,7, or 8 membered ring otherthan a 6-carbon aromatic ring, and (3) an aromatic ring, with theproviso that said 6, 7, or 8 membered ring (2), is fused to both thecyclopentadienyl ring (1), and the aromatic ring (3), said Cp* having upto 60 atoms other than hydrogen; p is 1 or 2; when p is 1, M* is analkali metal or an alkaline earth metal halide, and, when p is 2, M* isan alkaline earth metal; said M* being bound to at least one of thenon-fused, ring-carbons of the cyclopentadienyl ring, (1); Cp is thearomatic ligand group derived from Cp* by removal of M*; M is a metalselected from Groups 3-10 or the Lanthanide series of the Periodic Tableof the Elements; Z is either: a) a cyclic ligand group containingdelocalized it-electrons, including a second or third, fused, polycyclicligand, Cp, said Z being bonded to M by means of delocalized π-electronsand optionally also covalently bonded to Cp through a divalent bridginggroup, Z′, or b) a divalent moiety of the formula —Z′Y—, wherein, Z′ isSiR⁶ ₂, CR⁶ ₂, SiR⁶ ₂SiR⁶ ₂, CR⁶ ₂CR⁶ ₂, CR⁶CR⁶, CR⁶ ₂SiR⁶ ₂, BR⁶,BR⁶L″, or GeR⁶ ₂; Y is —O—, —S—, —NR⁵—, —PR⁵—; —NR⁵ ₂, or —PR⁵ ₂; R⁵,independently each occurrence, is hydrocarbyl, trihydrocarbylsilyl, ortrihydrocarbylsilylhydrocarbyl, said R⁵ having up to 20 atoms other thanhydrogen, and optionally two R⁵ groups or R⁵ together with Y form a ringsystem; R⁶, independently each occurrence, is hydrogen, or a memberselected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl,halogenated aryl, —NR⁵ ₂, and combinations thereof, said R⁶ having up to20 non-hydrogen atoms, and optionally, two groups form a ring system; L″is a monodentate or polydentate Lewis base optionally bonded to R⁶; X ishydrogen or a monovalent anionic ligand group having up to 60 atoms notcounting hydrogen; L independently each occurrence is a neutral ligatingcompound having up to 20 atoms, other than hydrogen, and optionally Land X are bonded together; X′ is a diavalent anionic ligand group havingup to 60 atoms other than hydrogen; z is 0, 1 or 2; x is 0, 1, 2, or 3;l is a number from 0 to 2; and x′ is 0 or
 1. 2. A compound or complexaccording to claim 1 corresponding to the formula:

structural isomers thereof wherein one or more double bonds occupydifferent positions within the various rings, and mixtures thereof,wherein: T independently each occurrence is carbon, silicon, nitrogen,phosphorus, oxygen, sulfur, or boron; J independently each occurrence ishydrogen, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylgermyl,halide, hydrocarbyloxy, trihydrocarbylsiloxy,bis(trihydrocarbylsilyl)amino, di(hydrocarbyl)amino,hydrocarbyleneamino, hydrocarbylimino, di(hydrocarbyl)phosphino,hydrocarbylenephosphino, hydrocarbylsulfido, halo-substitutedhydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl,trihydrocarbylsilyl-substituted hydrocarbyl,trihydrocarbylsiloxy-substituted hydrocarbyl,bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylenephosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said J group having up to 40atoms not counting hydrogen atoms, and optionally two J groups togetherform a divalent derivative thereby forming a saturated or unsaturatedring, with the proviso that, in at least one occurrence, two or more ofthe foregoing J groups on different atoms, at least one or which is T,together form a divalent derivative, thereby forming at least onearomatic ring that is fused to the 6, 7, or 8 membered ring; t is 0, 1or 2; and, for compounds of formula (1A₁) or (1A₂) where T is carbon, inat least one occurrence, t is 2; and M*, p, M, Z, X, L, X′, x, l, and x′are as previously defined in claim
 1. 3. A metal complex according toclaim 1, corresponding to the formula:

structural isomers thereof wherein one or more double bonds occupydifferent positions within the various rings, or a mixture thereof,wherein: T independently each occurrence is carbon, silicon, nitrogen,phosphorus, oxygen, sulfur, or boron; J independently each occurrence ishydrogen, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylgermyl,halide, hydrocarbyloxy, trihydrocarbylsiloxy,bis(trihydrocarbylsilyl)amino, di(hydrocarbyl)amino,hydrocarbyleneamino, hydrocarbylimino, di(hydrocarbyl)phosphino,hydrocarbylenephosphino, hydrocarbylsulfido, halo-substitutedhydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl,trihydrocarbylsilyl-substituted hydrocarbyl,trihydrocarbylsiloxy-substituted hydrocarbyl,bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylenephosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said J group having up to 40atoms not counting hydrogen atoms, and optionally two J groups togetherform a divalent derivative thereby forming a saturated or unsaturatedring, with the proviso that, in at least one occurrence, two or more ofthe foregoing J groups on different atoms, at least one or which is T,together form a divalent derivative, thereby forming at least onearomatic ring that is fused to the 6, 7, or 8 membered ring; t is 0, 1or 2; and, for compounds of formula (1A₁) or (1A₂) where T is carbon, inat least one occurrence, t is 2; and M, Z′, X, L, X′, x, l, and x′ areas previously defined in claim
 1. 4. A compound or complex according toclaim 1, corresponding to the formula:

structural isomers thereof wherein one or more double bonds occupydifferent positions within the various rings, and mixtures thereof,wherein J* independently each occurrence is hydrogen, hydrocarbyl,trihydrocarbylsilyl, trihydrocarbylgermyl, halide, hydrocarbyloxy,trihydrocarbylsiloxy, bis(trihydrocarbylsilyl)amino,di(hydrocarbyl)amino, hydrocarbyleneamino, hydrocarbylimino,di(hydrocarbyl)phosphino, hydrocarbylenephosphino, hydrocarbylsulfido,halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl,trihydrocarbylsilyl-substituted hydrocarbyl,trihydrocarbylsiloxy-substituted hydrocarbyl,bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl, di(hydrocarbyl)phosphinosubstituted hydrocarbyl, hydrocarbylenephosphino-substitutedhydrocarbyl, or hydrocarbylsulfido-substituted hydrocarbyl, said J*group having up to 40 atoms not counting hydrogen atoms, and two J*groups together or a J* and a J′ group together may form a divalentderivative thereby forming a saturated or unsaturated ring, with theproviso that, in at least one occurrence, two or more of the foregoingJ* groups on different atoms, together form a divalent derivative,thereby forming at least one aromatic ring that is fused to the 6, 7, or8 membered ring; J′ independently each occurrence is hydrogen,hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylgermyl, halide,hydrocarbyloxy, trihydrocarbylsiloxy, bis(trihydrocarbylsilyl)amino,di(hydrocarbyl)amino, hydrocarbyleneamino, hydrocarbylimino,di(hydrocarbyl)phosphino, hydrocarbylenephosphino, hydrocarbylsulfido,halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl,trihydrocarbylsilyl-substituted hydrocarbyl,trihydrocarbylsiloxy-substituted hydrocarbyl,bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylenephosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said J′ group having up to40 atoms not counting hydrogen atoms, and two J′ groups together or a J′group and a J* group together may form a divalent derivative therebyforming a saturated or unsaturated fused ring; M* is hydrogen, an alkalimetal or an alkaline earth metal halide, T is carbon, boron, nitrogen oroxygen, t is 1 or 2; t′ is 0, 1 or 2, and M, X, L, X′, x, l, and x′ areas defined in claim
 3. 5. A metal compound or complex according to claim4 corresponding to the formula:

wherein T is carbon, or nitrogen; when T is carbon, t′ is 2, and when Tis nitrogen, t′ is 1; M* is hydrogen, sodium, potassium, or lithium; Mis titanium; R¹ each occurrence is hydrogen or a hydrocarbyl, amino oramino-substituted hydrocarbyl group of up to 20 atoms other thanhydrogen, and optionally two R′ groups may be joined together; Y is —O—,—S—, —NR⁵-, —PR⁵-; —NR⁵ ₂, or —PR⁵ ₂; Z′ is SiR⁶ ₂, CR⁶ ₂, SiR⁶ ₂SiR⁶ ₂,CR⁶ ₂CR⁶ ₂, CR⁶═CR⁶, CR⁶ ₂SiR⁶ ₂, BR⁶, BR⁶L″, or GeR⁶ ₂; R⁵ eachoccurrence is independently hydrocarbyl, trihydrocarbylsilyl, ortrihydrocarbylsilylhydrocarbyl, said R⁵ having up to 20 atoms other thanhydrogen, and optionally two R⁵ groups or R⁵ together with Y form a ringsystem; R⁶ each occurrence is independently hydrogen, or a memberselected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl,halogenated aryl, —NR⁵ ₂, and combinations thereof, said R⁶ having up to20 non-hydrogen atoms, and optionally, two R⁶ groups form a ring system;X, L, L″,and X′ are as previously defined; x is 0, 1 or 2; l is 0 or 1;and x′ is 0 or 1; with the proviso that: when x is 2, X′ is zero, M isin the +4 formal oxidation state (or M is in the +3 formal oxidationstate if Y is —NR⁵ ₂ or —PR⁵ ₂), and X is an anionic ligand selectedfrom the group consisting of halide, hydrocarbyl, hydrocarbyloxy,di(hydrocarbyl)amido, di(hydrocarbyl)phosphido, hydrocarbylsulfido, andsilyl groups, as well as halo-, di(hydrocarbyl)amino-, hydrocarbyloxy-,and di(hydrocarbyl)phosphino-substituted derivatives thereof, said Xgroup having up to 30 atoms not counting hydrogen, when x is 0 and X′ is1, M is in the +4 formal oxidation state, and X′ is a dianionic ligandselected from the group consisting of hydrocarbadiyl, oxyhydrocarbylene,and hydrocarbylenedioxy groups, said X group having up to 30 nonhydrogenatoms, when x is 1, and X′ is 0, M is in the +3 formal oxidation state,and X is a stabilizing anionic ligand group selected from the groupconsisting of allyl, 2-(N,N-dimethylamino)phenyl,2-(N,N-dimethylaminomethyl)phenyl, and 2-(N,N-dimethylamino)benzyl, andwhen x and X′ are both 0, 1 is 1, M is in the +2 formal oxidation state,and L is a neutral, conjugated or nonconjugated diene, optionallysubstituted with one or more hydrocarbyl groups, said L having up to 40carbon atoms and being bound to M by means of delocalized π-electronsthereof.
 6. A metal complex according to claim 1 that is:(2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidetitanium (II) 1,4-diphenyl-1,3-butadiene,(2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidetitanium (II) 1,3-pentadiene,((2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidetitanium (III) 2-(N,N-dimethylamino)benzyl,(2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidetitanium (IV) dichloride,2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidetitanium (IV) dimethyl,2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidetitanium (IV) dibenzyl, (2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(cyclohexyl)dimethyl-silanamide titanium (II)1,4-diphenyl-1,3-butadiene,(2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(cyclohexyl)dimethyl-silanamidetitanium (II) 1,3-pentadiene,((2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(cyclohexyl)dimethyl-silanamidetitanium (III) 2-(N,N-dimethylamino)benzyl,(2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(cyclohexyl)dimethyl-silanamidetitanium (IV) dichloride,2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(cyclohexyl)dimethyl-silanamidetitanium (IV) dimethyl,2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(cyclohexyl)dimethyl-silanamidetitanium (IV) dibenzyl, (2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethyl-silanamide titanium (II)1,4-diphenyl-1,3-butadiene,(2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidetitanium (II) 1,3-pentadiene, ((2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethyl-silanamide titanium(III) 2-(N,N-dimethylamino)benzyl,(2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidetitanium (IV) dichloride,2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidetitanium (IV) dimethyl,2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethyl-silanamidetitanium (IV) dibenzyl,(2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(cyclohexyl)dimethyl-silanamidetitanium (II) 1,4-diphenyl-1,3-butadiene,(2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(cyclohexyl)dimethyl-silanamidetitanium (II) 1,3-pentadiene,((2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(cyclohexyl)dimethyl-silanamidetitanium (III) 2-(N,N-dimethylamino)benzyl,(2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(cyclohexyl)dimethyl-silanamidetitanium (IV) dichloride,2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(cyclohexyl)dimethyl-silanamidetitanium (IV) dimethyl,2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(cyclohexyl)dimethyl-silanamidetitanium (IV) dibenzyl, or a mixture thereof.